Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
  • F16L11/125—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting non-inflammable or heat-resistant hoses
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D22/00—Producing hollow articles
  • B29D22/003—Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/001—Combinations of extrusion moulding with other shaping operations
  • B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
  • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
  • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
  • F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
  • F02M37/0011—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor
  • F02M37/0017—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor related to fuel pipes or their connections, e.g. joints or sealings
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2022/00—Hollow articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/03—3 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/202—Conductive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/306—Resistant to heat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/558—Impact strength, toughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/726—Permeability to liquids, absorption
  • B32B2307/7265—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/40—Closed containers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2597/00—Tubular articles, e.g. hoses, pipes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer

Definitions

• the invention relates to a multilayer hollow body which has a very high washing resistance on the selection of the molding compositions of the individual layers used.
• the multilayer hollow body is primarily a hollow profile, such as a pipe, or a container for passing or storing liquid or gaseous media.
• polyamides are suitable as material both for the inner layer and for the outer layer.
• EVOH is incompatible with polyamides such as PA11, PA12, PA1012 or PA1212 and poorly tolerated with PA612.
• adhesion between the adjacent layers is indispensable and can thus be ensured only when an adhesion promoter layer is interposed.
• Solutions containing a primer layer based on, for example, polyolefins are therefore unsuitable because of their low heat resistance.
• an adhesion-promoting layer containing a polyamide selected from PA6, PA66 and PA6 / 66, optionally a polyamine-polyamide copolymer and a polyamide selected from PA11, PA12, PA612, PA1012 and PA1212.
• the object of the invention is to provide a composite of an EVOH layer and at least two polyamide layers, which has a high heat resistance and a high impact strength and in which, moreover, a good layer adhesion is obtained, the entire multilayer composite a high Washout has, ie Both insoluble and soluble extracts are after fuel contact at a very low level.
• the term "based on” here means that the respective molding composition at least 50 wt .-%, preferably at least 60 wt .-%, more preferably at least 65 wt .-% and particularly preferably at least 70 wt .-% of these polyamides or the polyamine Contains polyamide copolymers, each based on the total molding composition.
• further additives are generally included, which are described in more detail below, so that a total of 100 wt .-% results.
• the molding composition contains no further polyamides beyond.
• Standard layer structure means that not only the layer sequence and the composition of the layers are the same, but also that with different wall thickness, the individual layer thicknesses are converted to 1 mm total wall thickness.
• the inner layer (layer I) is intended to be in direct contact with the conveyed or stored medium.
• the multilayer hollow body is preferably a component of a fuel-carrying system, for example a fuel line or a fuel tank, wherein the fuel is furthermore preferably gasoline.
• the adhesion promoter layer (layer II) is especially optional if the molding compound of layer I contains PA610 and in particular if the polyamide of layer I consists of PA610, since in this case adhesion between layer I and layer III can be achieved sufficient for many applications. If layer I is based on one or more of the other polyamides claimed, layer II or an equivalent adhesion promoter layer is generally required.
• the layer I consists of a molding composition based on PA612, PA610, PA1010, PA1012 and / or PA1212 and copolymers thereof and mixtures thereof.
• the molding compound of layer II contains neither PA11 nor PA12.
• the polyamide of layer I is more preferably PA612.
• the molding compound of layer II contains as polyamide component a mixture of PA612 and PA6.
• At least 0.5 parts by weight, particularly preferably at least 10 parts by weight, particularly preferably at least 20 parts by weight and very particularly preferably at least 30 parts by weight, are preferably in the molding compound of layer II while the upper limit is preferably 70 parts by weight, and more preferably 60 parts by weight.
• component according to b) are in the molding composition of the layer II preferably at least 0.5 parts by weight, more preferably at least 2 parts by weight, more preferably at least 5 parts by weight and most preferably at least 10 parts by weight while the upper limit is preferably 80 parts by weight, more preferably 60 parts by weight, and most preferably 40 parts by weight.
• component according to c) are in the molding material of the layer II preferably at least 0.5 parts by weight, more preferably at least 10 parts by weight, more preferably at least 20 parts by weight and most preferably at least 30 parts by weight while the upper limit is preferably 70 parts by weight, and more preferably 60 parts by weight.
• the layers I, II and III directly follow one another.
• further layers which preferably consist of polyamide molding compounds, follow the layer III outwards.
• a layer IV connects to the outside, which contains the same polyamide combination as a layer II.
• a layer V of a polyamide molding compound which is based on the same polyamides as a layer I .; In this way, the mechanical properties required for the application are ensured and at the same time the layer III is effectively protected from the ingress of atmospheric moisture, which would reduce the barrier effect.
• a further layer of a polyamide molding compound which is based on a polyamide, which is good liable to EVOH.
• This polyamide is, for example, PA6, PA66 or PA6 / 66.
• Layer II is in the simplest case a blend of the components according to a) and c). Since these polymers are largely incompatible with each other, a sufficient adhesion promoter effect is achieved in the blend production under conventional processing temperatures, which leads to a physical mixture, only in a relatively narrow composition range. Better results are obtained when the polyamide blend is prepared under conditions where, to some extent, the two polyamides react with each other via the end groups or via transamidation reactions to block copolymers. For this purpose, temperatures above 250 ° C., preferably above 280 ° C. and more preferably above 300 ° C. and optionally the presence of catalysts such as hypophosphorous acid, dibutyltin oxide, triphenylphosphine or phosphoric acid are generally required.
• catalysts such as hypophosphorous acid, dibutyltin oxide, triphenylphosphine or phosphoric acid are generally required.
• polyamide blend prepared initially under customary processing conditions, which is subsequently subjected to solid phase postcondensation under conditions which are customary with polyamides.
• These are generally temperatures from 140 ° C to about 5K below the crystallite melting point T m , preferably temperatures from 150 ° C to about 10K below T m , with reaction times of 2 to 48 hours, preferably 4 to 36 hours and more preferably 6 up to 24 hours.
• one polyamide contains an excess of amino end groups and the other polyamide contains an excess of carboxyl end groups.
• a linking of the components according to a) and c) can also be achieved by adding a reactive compound which preferably links the polyamide end groups together, for example a bisoxazoline, biscarbodiimide, bisanhydride, diisocyanate or the corresponding compounds having three or more functional groups.
• a reactive compound which preferably links the polyamide end groups together for example a bisoxazoline, biscarbodiimide, bisanhydride, diisocyanate or the corresponding compounds having three or more functional groups.
• Another way to make the components according to a) and c) compatible with each other is the addition of an effective amount of the component according to b).
• PA6 is produced by ring-opening polymerization of caprolactam.
• PA66 is made by polycondensation of hexamethylenediamine and adipic acid. It is just like PA6 in a variety of types commercially available.
• PA6 / 66 is a copolycondensate starting from the monomers caprolactam, hexamethylenediamine and adipic acid.
• the amino group concentration of the polyamine-polyamide copolymer is in the range of 100 to 2500 mmol / kg.
• the polyamine has a number-average molecular weight M n of at most 20,000 g / mol, more preferably of not more than 10,000 g / mol and more preferably of not more than 5,000 g / mol.
• Lactams or ⁇ -aminocarboxylic acids which are used as polyamide-forming monomers contain 4 to 19 and in particular 6 to 12 carbon atoms.
• Caprolactam, ⁇ -aminocaproic acid, capryllactam, ⁇ -aminocaprylic acid, laurolactam, ⁇ -aminododecanoic acid and / or ⁇ -aminoundecanoic acid are particularly preferably used.
• Combinations of diamine and dicarboxylic acid are, for example, hexamethylenediamine / adipic acid, hexamethylenediamine / dodecanedioic acid, octamethylenediamine / sebacic acid, decamethylenediamine / sebacic acid, decamethylenediamine / dodecanedioic acid, dodecamethylenediamine / dodecanedioic acid and dodecamethylenediamine / 2,6-naphthalenedicarboxylic acid.
• decamethylenediamine / dodecanedioic acid / terephthalic acid hexamethylenediamine / adipic acid / terephthalic acid, hexamethylenediamine / adipic acid / caprolactam, decamethylenediamine / dodecanedioic acid / ⁇ -aminoundecanoic acid, decamethylenediamine / dodecanedioic acid / laurolactam, decamethylenediamine / terephthalic acid / laurolactam or dodecamethylene / 2,6-naphthalene dicarboxylic acid / laurolactam.
• the composition of the polyamide moiety can vary within a very wide range, since the compatibility with the polyamides of the components according to a) and c) is obviously determined by other factors and is generally present.
• the polyamine-polyamide copolymers can be prepared by various methods.
• lactam cleavage and prepolymerization are optionally carried out first in the presence of water (alternatively, the corresponding ⁇ -aminocarboxylic acids or diamines and dicarboxylic acids are used directly and prepolymerized); in the second step, the polyamine is added. It is then expanded at temperatures between 200 and 290 ° C and polycondensed in a stream of nitrogen or in vacuo.
• Another preferred method is the hydrolytic degradation of a polyamide to a prepolymer and simultaneous or subsequent reaction with the polyamine.
• polyamides are used in which the end group difference is approximately zero.
• Ultra-high-branched polyamides having acid numbers of less than 40 mmol / kg, preferably less than 20 mmol / kg and more preferably less than 10 mmol / kg, can be produced by these processes. Already after one to five hours reaction time at temperatures of 200 ° C to 290 ° C, a nearly complete conversion is achieved.
• the polyamine-polyamide copolymers according to the prior art can also be post-condensed in solid phase.
• PA11 is prepared by polycondensation of ⁇ -aminoundecanoic acid, while PA12 is obtained by ring-opening polymerization of laurolactam. Both polymers are commercially available in a variety of types.
• PA610 is prepared in a known manner by polycondensation of an equivalent mixture of hexamethylenediamine and 1,10-decanedioic acid
• PA612 is prepared in a known manner by polycondensation of an equivalent mixture of hexamethylenediamine and 1,12-dodecanedioic acid
• PA1010 by polycondensation of an equivalent mixture of 1,10-decanediamine and 1.10-decanedioic acid is produced.
• PA1012 is prepared by polycondensation of an equivalent mixture of 1.10-decanediamine and 1.12-dodecanedioic acid while PA1212 is similarly obtained from 1.12-dodecanediamine and 1.12-dodecanedioic acid.
• mixtures of different polyamides can also be used here, for. PA12 / PA1012 or PA12 / PA1212.
• Such mixtures are characterized by a particularly high low temperature impact toughness; for example, they are in the EP-A-0 388 583 described.
• the molding compositions contain an effective amount of an oxidation stabilizer, and more preferably an effective amount of an oxidation stabilizer in combination with the effective amount of a copper-containing stabilizer.
• Suitable oxidation stabilizers are, for example, aromatic amines, sterically hindered phenols, phosphites, phosphonites, thiosynergists, hydroxylamines, benzofuranone derivatives, acryloyl-modified phenols, etc.
• oxidation stabilizers are commercially available in a variety of types, for example under the trade names Naugard 445, Irganox 1010, Irganox 1098, Irgafos 168, P-EPQ or Lowinox DSTDP.
• the molding compositions contain from about 0.01 to about 2 weight percent, and preferably from about 0.1 to about 1.5 weight percent, of an oxidation stabilizer.
• the molding compositions may also contain a UV stabilizer or a light stabilizer of the HALS type.
• Suitable UV stabilizers are primarily organic UV absorbers, for example benzophenone derivatives, benzotriazole derivatives, oxalanilides or phenyltriazines.
• HALS type light stabilizers are tetramethylpiperidine derivatives; these are inhibitors which act as radical scavengers. UV stabilizers and light stabilizers can advantageously be used in combination. Both are commercially available in a variety of types; in terms of dosage, the manufacturer's instructions can be followed.
• the molding compositions may additionally contain a hydrolysis stabilizer such as a monomeric, oligomeric or polymeric carbodiimide or a bisoxazoline.
• a hydrolysis stabilizer such as a monomeric, oligomeric or polymeric carbodiimide or a bisoxazoline.
• polymers which may be included as an additive in the molding compositions are, for example, polyetheramides or polytetrafluoroethylene (PTFE).
• Toughening rubbers for polyamide molding compounds are state of the art. They contain functional groups derived from unsaturated functional compounds, which have either been polymerized into the main chain or grafted onto the main chain. The most common are EPM or EPDM rubber which has been radically grafted with maleic anhydride. Such rubbers can also be used together with an unfunctionalized polyolefin such.
• B. isotactic polypropylene are used, as in EP-A-0 683 210 described.
• Plasticizers and their use in polyamides are known.
• a general overview of plasticizers which are suitable for polyamides can be found in Gumbleter / Müller, Kunststoffadditive, C. Hanser Verlag, 2nd Edition, p. 296.
• plasticizers suitable conventional compounds are, for. B. esters of p-hydroxybenzoic acid having 2 to 20 carbon atoms in the alcohol component or amides of arylsulfonic acids having 2 to 12 carbon atoms in the amine component, preferably amides of benzenesulfonic acid.
• Suitable plasticizers include p-hydroxybenzoic acid ethyl ester, octyl p-hydroxybenzoate, i-hexadecyl p-hydroxybenzoate, n-octyltoluene sulfonamide, benzenesulfonic acid-n-butylamide or benzenesulfonic acid 2-ethylhexylamide.
• Suitable pigments and / or dyes are, for example, carbon black, iron oxide, zinc sulfide, ultramarine, nigrosine, pearlescent pigments and metal flakes.
• Additives which increase the electrical conductivity are, for example, conductivity black or carbon nanotubes.
• Suitable processing aids are, for example, paraffins, fatty alcohols, fatty acid amides, stearates such as calcium stearate, paraffin waxes, montanates or polysiloxanes.
• the molding compound is prepared from the individual components by mixing in the melt, as known to those skilled in the art.
• the layer III EVOH is a copolymer of ethylene and vinyl alcohol.
• the ethylene content in the copolymer is usually from 25 to 60 mol% and in particular from 28 to 45 mol%.
• a variety of types are commercially available. For example, reference is made to the company publication "Introduction to Kuraray EVAL TM Resins", version 1.2 / 9810 of the company Kuraray EVAL Europe.
• the molding compound may contain further additives in addition to the EVOH according to the prior art, such as they are common for barrier applications. Such additives are usually know-how of the EVOH supplier.
• the claimed low extract content is achieved by the selection of the polyamide and by the measure that the molding compound of layer I and preferably also the molding compound of layer II contains no plasticizer. Moreover, it is advantageous if the molding compound of layer I and preferably also the molding compound of layer II contains only the amount of stabilizers and processing aids that is needed at the moment.
• the multi-layer composite according to the invention When using the multi-layer composite according to the invention for the management or storage of combustible liquids, gases or dusts, such. As fuel or fuel vapor, it is advisable to equip one of the composite belonging layers electrically conductive. This can be done by compounding with an electrically conductive additive by all methods of the prior art.
• an electrically conductive additive there may be used, for example, carbon black, metal flakes, metal powders, metallized glass beads, metallized glass fibers, metal fibers (for example, stainless steel), metallized whiskers, carbon fibers (also metallized), intrinsically conductive polymers or graphite fibrils. It is also possible to use mixtures of different conductive additives.
• the electrically conductive layer is in direct contact with the medium to be fed or stored and has a surface resistivity of not more than 10 9 ⁇ / square, and preferably not more than 10 6 ⁇ / square.
• the measurement method for determining the resistance of multilayer pipes is explained in SAE J 2260 of November 2004. In this case, either the layer I as a whole is electrically conductive or the layer I consists of two sub-layers, one of which is electrically conductive and the other is not equipped electrically conductive.
• the sheath can be applied to the multi-layer composite both with and without the use of an additional adhesion promoter, for example by means of coextrusion, extrusion via a crosshead or in that a prefabricated elastomer hose is pushed over the finished extruded multilayer pipe.
• the sheath has a thickness of 0.1 to 4 mm, and preferably from 0.2 to 3 mm.
• Suitable elastomers are, for example, chloroprene rubber, ethylene / propylene rubber (EPM), ethylene / propylene / diene rubber (EPDM), epichlorohydrin rubber (ECO), chlorinated Polyethylene, acrylate rubber, chlorosulfonated polyethylene, silicone rubber, plasticized PVC, polyetheresteramides or polyetheramides.
• the multilayer composite can be produced in one or more stages, for example by single-stage injection molding, co-extrusion, coextrusion blow molding (for example 3D blow molding, tube extrusion into an opened mold, 3D tube manipulation, suction blow molding, 3D suction blow molding, sequential injection molding) Blow molding) or by multi-stage process, such. B. in the US 5 554 425 described.
• Comparative Example 1 (according to EP 1216826 A2, used in the automotive industry for fuel lines):
• the tube according to the invention therefore meets the requirements placed on fuel lines and has an outstanding washout resistance compared to currently used pipes.

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• 2016
  • 2016-09-21 EP EP16189917.4A patent/EP3299165B1/fr active Active
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